EP0540199B1 - Stable water in oil emulsions - Google Patents
Stable water in oil emulsions Download PDFInfo
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- EP0540199B1 EP0540199B1 EP92309182A EP92309182A EP0540199B1 EP 0540199 B1 EP0540199 B1 EP 0540199B1 EP 92309182 A EP92309182 A EP 92309182A EP 92309182 A EP92309182 A EP 92309182A EP 0540199 B1 EP0540199 B1 EP 0540199B1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4993—Derivatives containing from 2 to 10 oxyalkylene groups
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/10—Insect repellent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/13—Burn treatment
Definitions
- the present invention relates to water-in-oil emulsions containing surface active agents of polysiloxane. More particularly, the present invention relates to sunscreens and skin care lotions containing water-in-oil emulsions containing polysiloxane surface active agents having radial organic polyether groups.
- polysiloxane surface active agents containing radial organic polyether groups to stabilize silicone emulsions.
- U.S. Patent No. 4,265,878 uses a polysiloxane surface active agent to stabilize antiperspirant stick compositions.
- U.S. Patent No. 4,218,250 uses such a polysiloxane surface active agent to stabilize polish formulations.
- U.S. Patent No. 4,268,499 uses these surface active agents to stabilize antiperspirant emulsion compositions.
- U.S. Patent No. 4,311,695 uses such surface active agents in personal care creams and the like.
- the subject polysiloxane surface active agents are generically known and are sometimes referred to as siloxaneoxyalkylene copolymers.
- siloxaneoxyalkylene copolymers are generically known and are sometimes referred to as siloxaneoxyalkylene copolymers.
- their use to date has been directed to stabilizing silicone emulsions in skin care creams and antiperspirant sticks.
- their use in forming stable lotions has not been completely satisfactory, due to emulsion instability, because the variables affecting their function are not well understood.
- lotions are made using a lipophilic organic surfactant together with a lipophilic polysiloxane copolymer (e.g., U.S. 4,988,504) they show low emulsion stability and relatively low freeze/thaw resistance.
- an improved water-in-oil emulsion sunscreen or skin care lotion comprising (a) from 89.5 to 40 parts by weight of an aqueous solution as a discontinuous phase; (b) from 10 to 45 parts by weight of a volatile liquid having a normal boiling point of less than 250°C as a continuous phase, the volatile liquid being selected from the group of organosiloxane fluids having the average unit formula (CH 3 ) a SiO (4-a)/2 , wherein "a” has an average value of from 2 to 3, inclusive; (c) from 0.1 to 3 parts by weight of an organic oil-in-water type surfactant having an HLB value of from 8 to 18, inclusive; and (d) from 0.4 to 20 parts by weight of a polyorganosiloxane polyoxyalkylene copolymer surface active agent of the formula MD x D′ y M, wherein D is R 2 SiO 2/2 where R is hydrogen or a substituted or unsubstituted hydrocarbon radical of from
- the emulsions of the present invention are in the form of a lotion and preferably comprise an additive (e) selected from the group consisting of an antiperspirant, a humectant, an insect repellent, an odorant, a deodorant, an emollient, an antiseptic, a sunscreen agent, a cleansing agent, a suitable pharmaceutical, a pigment, a biocide, and mixtures of any of the foregoing.
- sunscreen agents such as titanium dioxide, UVA and UVB filters which are known to those skilled in the art and are available commercially.
- the UV filters are selected from para amino benzoic acid (PABA) and para amino benzoates, salicylates, cinnamates, benzophenones, anthranilates, dibenzoyl methanes, camphor derivatives and mixtures thereof.
- PABA para amino benzoic acid
- Suitable R groups include hydrogen, methyl, ethyl, vinyl, phenyl, trifluoropropyl, etc. Preferably, at least 80% by number of all R groups are methyl.
- R 2 may be -CH 2 -CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 C(CH 3 ) 2 -, -CH 2 CH 2 CH 2 CH 2 -, etc. However, it is preferred that at least 50% by number of R 2 units are -CH 2 CH 2 -.
- the number of repeating units of R′ i.e. the value of n, be between about 5 and 20.
- the molecular weight of R′ should be less than about 900.
- the preferred value of n is from 10 to 15, which likewise for ethylene oxide provides a molecular weight of R′ of no more than about 700.
- R 3 is the group which bonds the polyoxyalkylene segment to the polysiloxane.
- this group is derived from alpha-beta unsaturated carboxylic acids or alcohols.
- R 3 is -CH 2 CH 2 CH 2 -. Otherwise, "a" could be 0 and the segments joined by -O-, which is the product of a condensation reaction between a condensable substituent on the polysiloxane and a condensable end group on polyalkylene oxide.
- R 4 is the terminal group of the polyalkylene ether.
- the type of R 4 is not critical and may be selected from hydrogen, methyl, ethyl, propyl, butyl, phenyl, alkenyl, acetyl, etc.
- R 4 is hydrogen.
- the polysiloxane absent R′ should have a molecular weight between about 15,000 about 50,000 and preferably between 25,000 and 35,000.
- Component (a) of the present invention is the discontinuous phase.
- the discontinuous phase preferably comprises water.
- the discontinuous phase can comprise liquid media other than water.
- suitable liquid media are organic compounds such as alcohols, including methanol, ethanol, phenol, ethylene glycol, propylene glycol, glycerine, their partial ethers and partial esters; nitrogen compounds including amides such as formamide, acetamide, N,N-dimethyl formamide and urea; nitriles such as acetonitrile, and amines and their salts; acids such as formic acid, acetic acid, benzoic acid, stearic acid and ethylene diaminetetraacetic acid; and ethers such as furan, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether and their polymeric forms such as triethylene glycol diethyl ether. Mixtures of any of the foregoing and mixtures of any of them with water are contemplated by the present invention.
- Emulsion compositions of this invention wherein the aqueous phase comprises water and/or ethanol are particularly useful.
- water-in-oil emulsions are desirable from an economic, safety and environmental viewpoint as a means of preparing, storing, shipping and using efficacious components.
- emulsion compositions of aqueous or ethanol solutions have value as personal care compositions.
- the base oil or volatile liquid continuous phase (b) is generally a fluid selected from the organosiloxane fluids having a normal, i.e. atmospheric pressure, boiling point of less than 250°C.
- the volatile organosiloxane fluids have the average unit formula: R a SiO (4-a/2) wherein R is hydrogen or a substituted or unsubstituted hydrocarbon radical of from 1 to about 12 carbon atoms and "a" has an average value of from 2 to 3.
- R is methyl and the organosiloxane is selected from the group consisting of (CH 3 ) 3 SiO 1/2 , (CH 3 ) 2 SiO 2/2 , CH 3 SiO 3/2 and SiO 4/2 units.
- the volatile methylsiloxane fluid consists essentially of dimethylsiloxane units, and optionally, trimethylsiloxane units.
- volatile liquid (b) are the cyclic siloxanes of the general formula ((CH 3 ) 2 SiO) b and the linear siloxanes of the general formula (CH 3 ) 3 SiO((CH 3 ) 2 SiO) c Si(CH 3 ) 3 , and their mixtures, wherein b is an integer of from 3 to 6 and c is an integer of from 0 to 4.
- Component (c) are organic oil-in-water type surfactants. These can be any cationic, anionic or nonionic organic surfactant suitable for preparing emulsions of the oil-in-water type and having a hydrophilic-lipophilic balance, HLB, value of from 8 to 18, inclusive.
- HLB hydrophilic-lipophilic balance
- oil-in-water type surfactants include polyethoxylated quaternary ammonium salts and polyoxyethylene fatty amines as cationic surfactants, and polyethylene-glycol alkylethers, polyethylene-glycol alkylarylethers, polyethoxylated sorbitan monolaurate, polyethoxylated sorbitan monooleate, polyoxyethylene lanolin derivatives, and polyethoxylated fatty alcohols as nonionic surfactants. Mixtures of cationic and/or nonionic oil-in-water surfactants are also suitable.
- Suitable organic surfactants having an HLB value of from 8 to 18 may be found by consulting standard publications such as McCutcheon's "Detergents and Emulsifiers," 1975 North America Edition, MC Publishing Co., Glen Rock, NJ, 1975.
- Component (d) comprises polyorganosiloxane polyoxyalkylene copolymer surface active agents.
- the copolymer surface active agents useful in the practice of the present invention are of the general formula: MD x D′ y M wherein M, D, D′, x and y are as previously defined.
- the polysiloxane surface active agent may be prepared by well known methods.
- the preferred method is to introduce an alpha-beta unsaturated alcohol or carboxylic acid into the polymerization of alkylene glycols to produce a terminally unsaturated polyalkylene oxide.
- These terminally unsaturated polyalkylene glycols are subsequently added to silicon bonded hydrogens on suitable polysiloxanes.
- the addition reaction proceeds best in the presence of an active metal catalyst such as platinum.
- compositions of the present invention are generally prepared by first forming the aqueous phase A by mixing together components (a) and (c). Then the oily phase B is prepared by mixing together components (b) and (d). The additive (e) is then added to either phase A or B, depending upon the type of additive as known to those skilled in the art. The two phases are then mixed, preferably with high sheer agitation, to form an emulsion. Optionally, the emulsions may be further homogenized.
- the lotions of the present invention can then be used in a wide variety of end products depending upon the additives employed.
- the lotions may be formulated into skin care creams, suntan lotions, make-up, facial scrubs and cleansing creams.
- Preferred formulations are sunscreen lotions and personal care lotions. These may be formulated using the water-in-oil emulsions of the present invention.
- Such compositions contain (A) from about 89.5 to about 40 parts by weight water (B) from about 10 to about 45 parts by weight organosiloxane fluid, (C) from about 0.1 to about 3 parts by weight of an organic oil-in-water surfactant having an HLB value of 8 to 18, (D) from about 0.4 to about 20 parts by weight of polysiloxane surface active agent and (E) an effective amount of sunscreen or other desired skin care agent.
- a series of general skin care water-in-oil formulations were prepared using SF1228 combined with "POLYSORBATE 80" as the emulsifier system.
- the emulsions are prepared according to the following:
- Part A the oil phase, is prepared by mixing together 10 parts by weight SF-1228, a polyorganosiloxane polyoxyalkylene copolymer emulsifier, 6 parts by weight of SF-1202 , a cyclomethylsiloxane fluid, and 4 parts by weight of isopropyl myristate, a liquid ester emollient.
- Part B the aqueous phase, is prepared by mixing together 0.2 parts by weight of polysorbate 80, an organic oil-in-water surfactant, 3.0 parts by weight of propylene glycol, 1 part by weight of sodium chloride and 75.8 parts by weight of water.
- Part B is then added to Part A with high shear agitation in a vessel, at room temperature.
- the emulsion formed is then milled in a Gifford-Wood homogenizer to increase stability.
- Examples 2 and 3 are prepared according to the above procedure, varying the type of skin care additives.
- the compositional data is set forth below in Table 1.
- Table 1 SKIN CARE FORMULATIONS
- a Polyorganosiloxane Polyoxyalkylene copolymer
- General Electric Company b Cyclomethylsiloxane Fluid
- General Electric Company c Fluilan brand of lanolin made by Croda, Inc.
- d Methylsilox
- Example 1 The procedure of Example 1 is followed, except that various sunscreen additives are employed in the oil phase.
- various sunscreen additives are employed in the oil phase.
- two formulations similar to Example 4 are also prepared and tested back to back.
- no polysorbate 80 is added; and in Example B, polysorbate oleate (HLB 4.3) is employed in place of polysorbate 80 (HLB 15.0).
- the compositional data is set forth below in Table 2.
- Examples 4 and 5 showed excellent stability (no separation) during a stability test at 40°C for 60 days and also in testing at 4 freeze/thaw cycles.
- the formulations without the polysorbate 80 (Examples 4A* and 4B*) had unexpectedly lower viscosity than that of Example 4. Further, after 24 hours at 40°C, separation was noticeable in both Examples 4A* and 4B*, with Example 4B* being slightly worse than 4A*.
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Description
- The present invention relates to water-in-oil emulsions containing surface active agents of polysiloxane. More particularly, the present invention relates to sunscreens and skin care lotions containing water-in-oil emulsions containing polysiloxane surface active agents having radial organic polyether groups.
- The use of polysiloxane surface active agents containing radial organic polyether groups to stabilize silicone emulsions is well known. U.S. Patent No. 4,265,878 uses a polysiloxane surface active agent to stabilize antiperspirant stick compositions. U.S. Patent No. 4,218,250 uses such a polysiloxane surface active agent to stabilize polish formulations. U.S. Patent No. 4,268,499 uses these surface active agents to stabilize antiperspirant emulsion compositions. Further, U.S. Patent No. 4,311,695 uses such surface active agents in personal care creams and the like.
- Also, mention is made of U.S. Patent No. 4,980,156, which describes improved antiperspirant compositions comprising an emulsion of an aqueous astringent in a volatile silicone fluid. Further, special mention is made of U.S. Patent No. 4,988,506, which describes polysiloxane surface active agents having high molecular weight.
- The subject polysiloxane surface active agents are generically known and are sometimes referred to as siloxaneoxyalkylene copolymers. However, their use to date has been directed to stabilizing silicone emulsions in skin care creams and antiperspirant sticks. However, their use in forming stable lotions has not been completely satisfactory, due to emulsion instability, because the variables affecting their function are not well understood. As will be shown in the appended examples, if, instead of antiperspirant sticks, lotions are made using a lipophilic organic surfactant together with a lipophilic polysiloxane copolymer (e.g., U.S. 4,988,504) they show low emulsion stability and relatively low freeze/thaw resistance. Surprisingly, however, it has now been found that if a hydrophilic surfactant is used together with certain lipophilic polysiloxane copolymers, in lotions, long term stable emulsions with excellent resistance to freeze/thaw cycling are obtained.
- It is the object of the present invention to produce novel skin care and sunscreen lotions having superior emulsion stability containing surface active agents comprising an organic hydrophobic surfactant and a siloxane surfactant containing radial organic polyether groups.
- It is another object of the present invention to provide a water-in-oil silicone emulsion having excellent freeze-thaw stability.
- Briefly, there is provided by the present invention an improved water-in-oil emulsion sunscreen or skin care lotion comprising (a) from 89.5 to 40 parts by weight of an aqueous solution as a discontinuous phase; (b) from 10 to 45 parts by weight of a volatile liquid having a normal boiling point of less than 250°C as a continuous phase, the volatile liquid being selected from the group of organosiloxane fluids having the average unit formula (CH3)aSiO(4-a)/2, wherein "a" has an average value of from 2 to 3, inclusive; (c) from 0.1 to 3 parts by weight of an organic oil-in-water type surfactant having an HLB value of from 8 to 18, inclusive; and (d) from 0.4 to 20 parts by weight of a polyorganosiloxane polyoxyalkylene copolymer surface active agent of the formula MDxD′yM, wherein D is R2SiO2/2 where R is hydrogen or a substituted or unsubstituted hydrocarbon radical of from 1 to about 12 carbon atoms, D′ is RR′SiO2/2 where R is as defined above and R′ is a polyalkylene ether of the formula -R3 a-(OR2)n-OR4 where R2 is a -CH2-CH2- group, R3 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms, R4 is the same as R, n has a value of from 5 to 20, and a is 0 or 1; M represents trimethylsiloxy endcapping units, x is from 335 to 475, and y is from 4 to 23; with the proviso that the molecular weight of polysiloxane units D is from about 25,000 to about 35,000 and the weight ratio of D to D′ is from greater than 60/40 to 90/10.
- The emulsions of the present invention are in the form of a lotion and preferably comprise an additive (e) selected from the group consisting of an antiperspirant, a humectant, an insect repellent, an odorant, a deodorant, an emollient, an antiseptic, a sunscreen agent, a cleansing agent, a suitable pharmaceutical, a pigment, a biocide, and mixtures of any of the foregoing. Most preferred are sunscreen agents such as titanium dioxide, UVA and UVB filters which are known to those skilled in the art and are available commercially.
- Typically, the UV filters are selected from para amino benzoic acid (PABA) and para amino benzoates, salicylates, cinnamates, benzophenones, anthranilates, dibenzoyl methanes, camphor derivatives and mixtures thereof.
- Suitable R groups include hydrogen, methyl, ethyl, vinyl, phenyl, trifluoropropyl, etc. Preferably, at least 80% by number of all R groups are methyl.
- R2 may be -CH2-CH2-, -CH2CH(CH3)-, -CH2C(CH3)2-, -CH2CH2CH2CH2-, etc. However, it is preferred that at least 50% by number of R2 units are -CH2CH2-.
- It is preferred herein that the number of repeating units of R′, i.e. the value of n, be between about 5 and 20. Thus, in the case of ethylene oxide as the repeating unit, the molecular weight of R′ should be less than about 900. The preferred value of n is from 10 to 15, which likewise for ethylene oxide provides a molecular weight of R′ of no more than about 700.
- R3 is the group which bonds the polyoxyalkylene segment to the polysiloxane. Preferably, this group is derived from alpha-beta unsaturated carboxylic acids or alcohols. Thus, R3 may be -CH2CH2CH2-, -CH2CH2-, -CH2CH2CH2CH2-, -(CH2)10(C=O)- etc. Preferably, R3 is -CH2CH2CH2-. Otherwise, "a" could be 0 and the segments joined by -O-, which is the product of a condensation reaction between a condensable substituent on the polysiloxane and a condensable end group on polyalkylene oxide.
- R4 is the terminal group of the polyalkylene ether. The type of R4 is not critical and may be selected from hydrogen, methyl, ethyl, propyl, butyl, phenyl, alkenyl, acetyl, etc. Preferably, R4 is hydrogen.
- The polysiloxane absent R′ should have a molecular weight between about 15,000 about 50,000 and preferably between 25,000 and 35,000.
- Component (a) of the present invention is the discontinuous phase. The discontinuous phase preferably comprises water.
- However, it is also contemplated that the discontinuous phase can comprise liquid media other than water. Suitable liquid media are organic compounds such as alcohols, including methanol, ethanol, phenol, ethylene glycol, propylene glycol, glycerine, their partial ethers and partial esters; nitrogen compounds including amides such as formamide, acetamide, N,N-dimethyl formamide and urea; nitriles such as acetonitrile, and amines and their salts; acids such as formic acid, acetic acid, benzoic acid, stearic acid and ethylene diaminetetraacetic acid; and ethers such as furan, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether and their polymeric forms such as triethylene glycol diethyl ether. Mixtures of any of the foregoing and mixtures of any of them with water are contemplated by the present invention.
- Emulsion compositions of this invention wherein the aqueous phase comprises water and/or ethanol are particularly useful. In common with oil-in-water emulsions, water-in-oil emulsions are desirable from an economic, safety and environmental viewpoint as a means of preparing, storing, shipping and using efficacious components. In addition, emulsion compositions of aqueous or ethanol solutions have value as personal care compositions.
- The base oil or volatile liquid continuous phase (b) is generally a fluid selected from the organosiloxane fluids having a normal, i.e. atmospheric pressure, boiling point of less than 250°C. The volatile organosiloxane fluids have the average unit formula:
RaSiO(4-a/2)
wherein R is hydrogen or a substituted or unsubstituted hydrocarbon radical of from 1 to about 12 carbon atoms and "a" has an average value of from 2 to 3. Preferably, R is methyl and the organosiloxane is selected from the group consisting of (CH3)3SiO1/2, (CH3)2SiO2/2, CH3SiO3/2 and SiO4/2 units. Preferably, the volatile methylsiloxane fluid consists essentially of dimethylsiloxane units, and optionally, trimethylsiloxane units. Of particular value as volatile liquid (b) are the cyclic siloxanes of the general formula ((CH3)2SiO)b and the linear siloxanes of the general formula (CH3)3SiO((CH3)2SiO)cSi(CH3)3, and their mixtures, wherein b is an integer of from 3 to 6 and c is an integer of from 0 to 4. A highly preferred methylsiloxane fluid is a mixture of the cyclic siloxanes wherein a major portion is tetramer, i.e. b=4. - Component (c) are organic oil-in-water type surfactants. These can be any cationic, anionic or nonionic organic surfactant suitable for preparing emulsions of the oil-in-water type and having a hydrophilic-lipophilic balance, HLB, value of from 8 to 18, inclusive. Examples of oil-in-water type surfactants include polyethoxylated quaternary ammonium salts and polyoxyethylene fatty amines as cationic surfactants, and polyethylene-glycol alkylethers, polyethylene-glycol alkylarylethers, polyethoxylated sorbitan monolaurate, polyethoxylated sorbitan monooleate, polyoxyethylene lanolin derivatives, and polyethoxylated fatty alcohols as nonionic surfactants. Mixtures of cationic and/or nonionic oil-in-water surfactants are also suitable. Other examples of suitable organic surfactants having an HLB value of from 8 to 18 may be found by consulting standard publications such as McCutcheon's "Detergents and Emulsifiers," 1975 North America Edition, MC Publishing Co., Glen Rock, NJ, 1975.
- Component (d) comprises polyorganosiloxane polyoxyalkylene copolymer surface active agents. The copolymer surface active agents useful in the practice of the present invention are of the general formula:
MDxD′yM
wherein M, D, D′, x and y are as previously defined. - The polysiloxane surface active agent may be prepared by well known methods. The preferred method is to introduce an alpha-beta unsaturated alcohol or carboxylic acid into the polymerization of alkylene glycols to produce a terminally unsaturated polyalkylene oxide. These terminally unsaturated polyalkylene glycols are subsequently added to silicon bonded hydrogens on suitable polysiloxanes. The addition reaction proceeds best in the presence of an active metal catalyst such as platinum.
- The manufacture of the polysiloxane surface active agents is well known and understood by those skilled in the art. Methods of preparation are taught in U.S. Patent Nos. 4,265,878; Re 25,727; 3,174,987; 4,122,029, and 1,172,899, all of which are hereby incorporated by reference.
- The compositions of the present invention are generally prepared by first forming the aqueous phase A by mixing together components (a) and (c). Then the oily phase B is prepared by mixing together components (b) and (d). The additive (e) is then added to either phase A or B, depending upon the type of additive as known to those skilled in the art. The two phases are then mixed, preferably with high sheer agitation, to form an emulsion. Optionally, the emulsions may be further homogenized.
- The lotions of the present invention can then be used in a wide variety of end products depending upon the additives employed. Typically, the lotions may be formulated into skin care creams, suntan lotions, make-up, facial scrubs and cleansing creams.
- Preferred formulations are sunscreen lotions and personal care lotions. These may be formulated using the water-in-oil emulsions of the present invention. Such compositions contain (A) from about 89.5 to about 40 parts by weight water (B) from about 10 to about 45 parts by weight organosiloxane fluid, (C) from about 0.1 to about 3 parts by weight of an organic oil-in-water surfactant having an HLB value of 8 to 18, (D) from about 0.4 to about 20 parts by weight of polysiloxane surface active agent and (E) an effective amount of sunscreen or other desired skin care agent.
- The following examples illustrate the present invention. They are not to be construed to limit the claims in any manner whatsoever.
- A series of general skin care water-in-oil formulations were prepared using SF1228 combined with "POLYSORBATE 80" as the emulsifier system.
- The emulsions are prepared according to the following: Part A, the oil phase, is prepared by mixing together 10 parts by weight SF-1228, a polyorganosiloxane polyoxyalkylene copolymer emulsifier, 6 parts by weight of SF-1202 , a cyclomethylsiloxane fluid, and 4 parts by weight of isopropyl myristate, a liquid ester emollient. Part B, the aqueous phase, is prepared by mixing together 0.2 parts by weight of polysorbate 80, an organic oil-in-water surfactant, 3.0 parts by weight of propylene glycol, 1 part by weight of sodium chloride and 75.8 parts by weight of water.
- Part B is then added to Part A with high shear agitation in a vessel, at room temperature. The emulsion formed is then milled in a Gifford-Wood homogenizer to increase stability.
- Examples 2 and 3 are prepared according to the above procedure, varying the type of skin care additives. The compositional data is set forth below in Table 1.
TABLE 1 SKIN CARE FORMULATIONS Examples 1 2 3 Part A, pbw SF-1228a 10.0 10.0 10.0 SF-1202b 6.0 5.0 7.0 Isopropyl Myristate 4.0 4.0 - Lanolinc - 1.5 1.0 SS-4267d - - 3.0 Part B, pbw Polysorbate 80e 0.2 0.2 0.2 Glycerine - 3.0 3.0 Propylene glycol 3.0 - - Sodium Chloride 1.0 1.0 1.0 Water 75.8 75.3 74.8 a = Polyorganosiloxane Polyoxyalkylene copolymer, General Electric Company b = Cyclomethylsiloxane Fluid, General Electric Company c = Fluilan brand of lanolin made by Croda, Inc. d = Methylsiloxane Fluid and Methylsiloxane resin e = Ethoxylated sorbitan oleate - All formulations passed 60 days at 40°C stability testing and 4 freeze/thaw cycles at -10 °C for 8 hours and 25 °C for 16 hours.
- The procedure of Example 1 is followed, except that various sunscreen additives are employed in the oil phase. For comparative purposes, two formulations similar to Example 4 are also prepared and tested back to back. In Example A, no polysorbate 80 is added; and in Example B, polysorbate oleate (HLB 4.3) is employed in place of polysorbate 80 (HLB 15.0). The compositional data is set forth below in Table 2.
TABLE 2 SUN PROTECTION FORMULATIONS Example 4A* 4B* 4 5 Part A, pbw SF-1228a 10.0 10.0 10.0 100 SF-1202b 12.0 12.0 12.0 100 Octyl salicylate - - - 30 Lonzest 143-Sc - - - 30 Lanolind 0.5 0.5 0.5 - Neoheliopan AVe 5.0 5.0 5.0 60 Micronized Titanium Dioxide 3.0 3.0 3.0 30 SS-4267f 3.0 3.0 3.0 - Mineral Oil (70 SUSg) 1.0 1.0 1.0 - Sorbitan Oleate - 0.2 - - Part B, pbw Polysorbate 80 - - 0.2 02 Glycerine 3.0 3.0 3.0 30 Sodium Chloride 1.0 1.0 1.0 10 Water 61.5 61.3 61.3 608 * = Comparative Example a = Polyorganosiloxane polyoxyalkylene copolymer, General Electric Company b = Cyclomethylsiloxane fluid, General Electric Company c = Lonza, Inc. brand of myristal proprionate d = Croda, Inc. brand of lanolin e = Haarmann and Reiner Corp. brand of octylmethoxycinnamate f = Methylsiloxane Fluid and Methyl Siloxane Resin g = SUS is Saybolt Universal Seconds visocity measurement - The formulations within the scope of the appended claims (Examples 4 and 5) showed excellent stability (no separation) during a stability test at 40°C for 60 days and also in testing at 4 freeze/thaw cycles. The formulations without the polysorbate 80 (Examples 4A* and 4B*) had unexpectedly lower viscosity than that of Example 4. Further, after 24 hours at 40°C, separation was noticeable in both Examples 4A* and 4B*, with Example 4B* being slightly worse than 4A*.
- The above-mentioned patents are hereby incorporated by reference.
Claims (10)
- A water-in-oil emulsion having improved stability comprising :(a) from 89.5 to 40 parts by weight of an aqueous solution as a discontinuous phase;(b) from 10 to 45 parts by weight of a volatile liquid having a normal boiling point of less than 250°C as a continuous phase, said volatile liquid being selected from the group consisting of organosiloxane fluids having the average unit formula
(CH3)aSiO(4-a)/2 (I)
wherein a has an average value of from 2 to 3, inclusive;(c) from 0.1 to 3 parts by weight of an organic oil-in-water type surfactant having an HLB value of from 8 to 18 inclusive; and(d) from 0.4 to 20 parts by weight of a polyorganosiloxane polyoxyalkylene copolymer surface active agent of the formula
MDxD'yM (II)
wherein
D is R2SiO2/2 where R is hydrogen or a substituted or unsubstituted hydrocarbon radical of from 1 to 12 carbon atoms;
D′ is RR′SiO2/2 where R′ is a polyalkylene ether of the formula
-R3 a - (OR2)n - OR4 (III)
where R2 is a -CH2 - CH2 - group, R3 is a substituted or unsubstituted alkylene group of 1 to 20 atoms, R4 is the same as R, n has a value of from 5 to 20, and a is 0 or 1;M is trimethylsiloxy endcapping units;x is from 335 to 475; andy is from 4 to 23;with the proviso that the molecular weight of polysiloxane units D is from about 25,000 to about 35,000 and the weight ratio of D to D′ is from greater than 60/40 to 90/10. - A composition as defined in Claim 1, wherein said aqueous phase comprises a liquid selected from the group consisting of water, methanol, ethanol, phenol, ethylene glycol, propylene glycol, glycerine, formamide, acetamide, N,N-dimethyl formamide, urea, acetonitrile, formic acid, acetic acid, benzoic acid, stearic acid, ethylenediaminetetraacetic acid, furan, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, and mixtures of any of the foregoing.
- A composition as defined in Claim 1, wherein said organosiloxane comprises units wherein R of formula I is methyl.
- A composition as defined in Claim 3, wherein said organosiloxane is selected from the group consisting of cyclic siloxanes of the general formula ((CH3)2SiO)b wherein b is an integer of from 3 to 6 and linear siloxanes of the general formula (CH3)3SiO((CH3)2SiO)cSi(CH3)3 wherein c is an integer of from 0 to 4.
- A composition as defined in Claim 4, wherein said organosiloxane is a mixture of cyclic methylsiloxanes wherein a major portion is tetramer, b=4.
- A composition as defined in Claim 1, wherein said polyorganosiloxane polyoxyalkylene copolymer has a molecular weight ranging from about 25,000 to about 35,000.
- A composition as defined in Claim 1, wherein said R of formula (II) is selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbons having from 1 to about 12 carbon atoms.
- A composition as defined in Claim 1, wherein said R3 of formula (III) is derived from alpha-beta unsaturated carboxylic acids or alcohols.
- A composition as defined in Claim 1 which is in the form of a lotion.
- A composition as defined in Claim 9 which further comprises (e) an additive selected from the group consisting of an antiperspirant, a humectant, an insect repellent, an odorant, a deodorant, an emollient, an antiseptic, a sunscreen agent, a cleansing agent, a suitable pharmaceutical, a pigment, a biocide and mixtures of any of the foregoing.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/773,838 US5292503A (en) | 1991-10-09 | 1991-10-09 | Stable water in oil emulsions |
US773838 | 1991-10-09 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0540199A2 EP0540199A2 (en) | 1993-05-05 |
EP0540199A3 EP0540199A3 (en) | 1994-01-12 |
EP0540199B1 true EP0540199B1 (en) | 1996-09-11 |
Family
ID=25099474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92309182A Expired - Lifetime EP0540199B1 (en) | 1991-10-09 | 1992-10-08 | Stable water in oil emulsions |
Country Status (7)
Country | Link |
---|---|
US (1) | US5292503A (en) |
EP (1) | EP0540199B1 (en) |
JP (1) | JPH05213715A (en) |
KR (1) | KR100233322B1 (en) |
CA (1) | CA2077827A1 (en) |
DE (1) | DE69213649T2 (en) |
ES (1) | ES2093212T3 (en) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180127B1 (en) * | 1992-06-16 | 2001-01-30 | Aquasource, Inc. | Slow release insect repellents |
US5393452A (en) * | 1992-11-09 | 1995-02-28 | General Electric Company | 2 in 1 shampoo system and conditioner comprising a silicon-polyether copolymer |
DE4243272A1 (en) * | 1992-12-21 | 1994-06-23 | Henkel Kgaa | Process for the preparation of oil-in-water emulsions |
GB2291658B (en) * | 1994-07-23 | 1998-08-12 | Ciba Geigy Ag | Aqueous textile treatment compositions containing an ultra-violet absorbing agent |
HU221029B1 (en) * | 1994-11-09 | 2002-07-29 | The Procter & Gamble Co. | Cleaning tissue treated with water-in-lipid emulsion for removal of perianal soils and process for its producing |
US5585092A (en) * | 1995-04-13 | 1996-12-17 | The Procter & Gamble Company | Gel deodorant compositions |
US5948540A (en) * | 1995-04-27 | 1999-09-07 | The Procter & Gamble Company | Carrier substrate treated with high internal phase inverse emulsions made with an organopolysiloxane-polyoxyalkylene emulsifier |
BR9608101A (en) * | 1995-04-27 | 1999-02-09 | Procter & Gamble | Carrier substrate treated with high internal water phase reverse emulsion |
US5725845A (en) * | 1995-11-03 | 1998-03-10 | Revlon Consumer Products Corporation | Transfer resistant cosmetic stick compositions with semi-matte finish |
US5980922A (en) * | 1996-04-30 | 1999-11-09 | Procter & Gamble Company | Cleaning articles treated with a high internal phase inverse emulsion |
US5763332A (en) * | 1996-04-30 | 1998-06-09 | The Procter & Gamble Company | Cleaning articles comprising a polarphobic region and a high internal phase inverse emulsion |
US5770183A (en) * | 1996-08-01 | 1998-06-23 | Linares; Francisco J. | High SPF (30 and over) waterproof sunblock compositions |
US5908707A (en) * | 1996-12-05 | 1999-06-01 | The Procter & Gamble Company | Cleaning articles comprising a high internal phase inverse emulsion and a carrier with controlled absorbency |
US6133166A (en) * | 1997-07-01 | 2000-10-17 | The Procter & Gamble Company | Cleaning articles comprising a cellulosic fibrous structure having discrete basis weight regions treated with a high internal phase inverse emulsion |
JP2001512178A (en) * | 1997-07-31 | 2001-08-21 | ザ、プロクター、エンド、ギャンブル、カンパニー | Wet cleaning products |
US6007797A (en) * | 1998-08-06 | 1999-12-28 | Ipa, Llc | Disappearing color sunscreen compositions |
US6387382B1 (en) | 1998-11-23 | 2002-05-14 | Axiom Laboratories, Inc. | Water-proof, respirable, skin barrier composition |
US6165450A (en) * | 1999-05-03 | 2000-12-26 | Em Industries, Inc. | Sprayable sunscreen compositions |
US6468511B1 (en) | 2000-05-19 | 2002-10-22 | Colgate-Palmolive Company | Emulsions with naphthalate esters |
US6403067B1 (en) | 2000-05-19 | 2002-06-11 | Colgate-Palmolive Company | Stable emulsions for cosmetic products |
US6403069B1 (en) | 2000-10-20 | 2002-06-11 | Colgate-Palmolive Company | High oil clear emulsion with elastomer |
US6387357B1 (en) | 2000-10-20 | 2002-05-14 | Colgate-Palmolive Company | High oil clear emulsion with diene elastomer |
CN1701114A (en) * | 2001-06-22 | 2005-11-23 | 宝洁公司 | Compositions for lipophilic fluid systems |
US10000693B2 (en) * | 2013-03-14 | 2018-06-19 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9868893B2 (en) * | 2013-03-14 | 2018-01-16 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US11180690B2 (en) | 2013-03-14 | 2021-11-23 | Flotek Chemistry, Llc | Diluted microemulsions with low surface tensions |
US9801626B2 (en) | 2013-04-16 | 2017-10-31 | Ethicon Llc | Modular motor driven surgical instruments with alignment features for aligning rotary drive shafts with surgical end effector shafts |
US9993258B2 (en) | 2015-02-27 | 2018-06-12 | Ethicon Llc | Adaptable surgical instrument handle |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0373424A2 (en) * | 1988-12-12 | 1990-06-20 | General Electric Company | Antiperspirant compositions |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3836647A (en) * | 1970-10-22 | 1974-09-17 | Dow Corning | Wash-resistant skin preparation |
US4218250A (en) * | 1978-09-28 | 1980-08-19 | Dow Corning Corporation | Polish formulations |
US4268499A (en) * | 1979-06-07 | 1981-05-19 | Dow Corning Corporation | Antiperspirant emulsion compositions |
US4265878A (en) * | 1979-06-07 | 1981-05-05 | Dow Corning Corporation | Antiperspirant stick compositions |
US4311695A (en) * | 1979-12-03 | 1982-01-19 | Dow Corning Corporation | Personal-care emulsions comprising a siloxane-oxyalkylene copolymer |
US4421656A (en) * | 1981-12-31 | 1983-12-20 | Dow Corning Corporation | Silicone emulsifier composition, invert emulsions therefrom and method therefor |
JP2691729B2 (en) * | 1987-06-23 | 1997-12-17 | 株式会社資生堂 | Solid water-in-oil emulsified cosmetic |
US4988504A (en) * | 1987-08-19 | 1991-01-29 | General Electric Company | Silicone surfactants |
US5036108A (en) * | 1988-12-14 | 1991-07-30 | Kao Corporation | Water-in-oil emulsion cosmetic |
US5008103A (en) * | 1988-12-29 | 1991-04-16 | General Electric Company | Silicone surfactants |
-
1991
- 1991-10-09 US US07/773,838 patent/US5292503A/en not_active Expired - Lifetime
-
1992
- 1992-09-09 CA CA002077827A patent/CA2077827A1/en not_active Abandoned
- 1992-10-08 KR KR1019920018456A patent/KR100233322B1/en not_active IP Right Cessation
- 1992-10-08 DE DE69213649T patent/DE69213649T2/en not_active Expired - Fee Related
- 1992-10-08 ES ES92309182T patent/ES2093212T3/en not_active Expired - Lifetime
- 1992-10-08 EP EP92309182A patent/EP0540199B1/en not_active Expired - Lifetime
- 1992-10-08 JP JP4269018A patent/JPH05213715A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0373424A2 (en) * | 1988-12-12 | 1990-06-20 | General Electric Company | Antiperspirant compositions |
Also Published As
Publication number | Publication date |
---|---|
JPH05213715A (en) | 1993-08-24 |
DE69213649T2 (en) | 1997-03-27 |
CA2077827A1 (en) | 1993-04-10 |
US5292503A (en) | 1994-03-08 |
EP0540199A3 (en) | 1994-01-12 |
ES2093212T3 (en) | 1996-12-16 |
KR930007434A (en) | 1993-05-20 |
DE69213649D1 (en) | 1996-10-17 |
EP0540199A2 (en) | 1993-05-05 |
KR100233322B1 (en) | 1999-12-01 |
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